Krishnan V Mahesh, Arman Hadi D, Tonzetich Zachary J
Department of Chemistry, University of Texas at San Antonio(UTSA), San Antonio, TX 78249, USA.
Dalton Trans. 2018 Jan 30;47(5):1435-1441. doi: 10.1039/c7dt04339b.
The synthesis of a square-planar cobalt(ii) hydrido complex supported by a pyrrole-based PNP ligand has been reinvestigated and its reactivity with various small molecules examined. Preparation of the complex was accomplished by treatment of the corresponding chloride complex, [CoCl(PNP)] (PNP = anion of 2,5-bis((di-tert-butylphosphino)methyl)pyrrole), with di-iso-butylaluminum hydride (DIBAL). Reaction of [CoCl(PNP)] with other hydride sources such as NaEtBH and LiAlH resulted in mixtures of the desired Co(ii) hydride along with the reduced Co(i) species, [Co(N)(PNP)], as the primary product. The hydride complex exhibits facile migratory insertion chemistry with CO producing the corresponding Co(ii) formate complex. When the Co-H complex is reacted with nitric oxide, the first example of a cobalt nitrosyl hydride complex is produced.
对由吡咯基PNP配体支撑的平面正方形钴（II）氢化物配合物的合成进行了重新研究，并考察了其与各种小分子的反应活性。该配合物的制备是通过用二异丁基氢化铝（DIBAL）处理相应的氯化物配合物[CoCl(PNP)]（PNP = 2,5-双（（二叔丁基膦基）甲基）吡咯的阴离子）来完成的。[CoCl(PNP)]与其他氢化物源如NaEtBH和LiAlH反应，得到所需的钴（II）氢化物与还原的钴（I）物种[Co(N)(PNP)]的混合物，[Co(N)(PNP)]是主要产物。该氢化物配合物与CO表现出容易的迁移插入化学，生成相应的钴（II）甲酸盐配合物。当Co-H配合物与一氧化氮反应时，生成了首例钴亚硝酰氢化物配合物。
